EP0487103B1 - Verfahren zur Herstellung von Arylensulfidpolymer - Google Patents

Verfahren zur Herstellung von Arylensulfidpolymer Download PDF

Info

Publication number
EP0487103B1
EP0487103B1 EP91119960A EP91119960A EP0487103B1 EP 0487103 B1 EP0487103 B1 EP 0487103B1 EP 91119960 A EP91119960 A EP 91119960A EP 91119960 A EP91119960 A EP 91119960A EP 0487103 B1 EP0487103 B1 EP 0487103B1
Authority
EP
European Patent Office
Prior art keywords
polymerization
polymer
carbon atoms
arylene sulfide
dichlorobenzene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP91119960A
Other languages
English (en)
French (fr)
Other versions
EP0487103A1 (de
Inventor
Carlton Edwin Ash
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Phillips Petroleum Co
Original Assignee
Phillips Petroleum Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Phillips Petroleum Co filed Critical Phillips Petroleum Co
Publication of EP0487103A1 publication Critical patent/EP0487103A1/de
Application granted granted Critical
Publication of EP0487103B1 publication Critical patent/EP0487103B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/0204—Polyarylenethioethers
    • C08G75/025—Preparatory processes
    • C08G75/0259—Preparatory processes metal hydrogensulfides

Definitions

  • This invention relates to the production of arylene sulfide polymers. In one aspect, this invention relates to the production of phenylene sulfide polymers. In another aspect, this invention relates to the production of arylene sulfide polymers having a high extrusion rate or a low inherent viscosity. In a further aspect, this invention relates to the production of arylene sulfide polymers in which the functionality of the polymer end groups is controllable. In a still further aspect, this invention relates to arylene sulfide polymers having alkyl, alkenyl, functionalized alkyl or functionalized alkenyl end groups.
  • Arylene sulfide polymers can be characterized at least in part in terms of a melt flow rate. It is generally considered that a melt flow rate is inversely related to molecular weight for polymeric materials in general and for arylene sulfide polymers in particular. Extrusion rate, which is more specifically defined hereinafter, is a specific type of melt flow rate which is particularly useful for characterizing arylene sulfide polymers in the lower molecular weight range.
  • Arylene sulfide polymers can also be characterized at least in part in terms of inherent viscosity. It is generally considered that inherent viscosity, which is more specifically defined hereinafter, is directly related to molecular weight for polymeric materials in general and for arylene sulfide polymers in particular.
  • Arylene sulfide polymers having a relatively high extrusion rate or relatively low inherent viscosity are desirable for a variety of applications such as encapsulation of electronic components and coating formulations.
  • US-A-4,437,182 and 4,482,665 provide exemplary disclosures of compositions comprising arylene sulfide polymers which are employed in the encapsulation of electronic components.
  • Arylene sulfide polymers in which the functionality of the polymer end groups is controllable are desirable for improving adhesion of the polymer to metal substrates and/or fiber reinforcement. Such polymers are also desirable for use in the preparation of copolymers by reaction at the polymer end groups having the desired functionality. The copolymers would be particularly useful as compatabilizers in polymer blends.
  • a process for preparing arylene sulfide polymers comprises contacting at least one sulfur source, at least one cyclic organic amide, and at least one dihaloaromatic compound to form a polymerization mixture, subjecting the polymerization mixture to polymerization conditions of temperature and time sufficient to form the arylene sulfide polymer, and recovering the arylene sulfide polymer, wherein the process is conducted in the presence of a suitable olefin.
  • the olefin may be added to the polymerization mixture prior to subjecting the polymerization mixture to polymerization conditions, or during the time the polymerization mixture is being subjected to polymerization conditions.
  • an arylene sulfide polymer composition comprising end groups resulting from polymerization in the presence of suitable olefins selected from the group consisting of alkyl radicals, alkenyl radicals, functionalized alkyl radicals, functionalized alkenyl radicals and combinations thereof.
  • This invention relates to arylene sulfide polymer compositions and a process for preparing arylene sulfide polymers having a readily controllable molecular weight as measured by extrusion rate or inherent viscosity and/or polymer end group functionality which is readily controllable comprising the steps of: (a) dehydrating an aqueous mixture comprising at least one sulfur source and at least one cyclic organic amide thereby forming a dehydrated mixture, (b) contacting at least one dihaloaromatic compound with the dehydrated mixture to produce a polymerization mixture, (c) subjecting the polymerization mixture to polymerization conditions of temperature and time sufficient to form the arylene sulfide polymer, and (d) recovering the arylene sulfide polymer, wherein the process is conducted in the presence of an olefin having 2 to about 20 carbon atoms.
  • the arylene sulfide polymers having a relatively high extrusion rate or low inherent viscosity made according to this invention are readily recoverable and well suited for use in applications where such relatively high extrusion rate or low inherent viscosity arylene sulfide polymers are desired, e.g. encapsulation of electronic components and coatings.
  • the arylene sulfide polymers having polymer end groups of desired functionality made according to this invention are readily recoverable and well suited for use in applications where such polymer end group functionality is desired, e.g. improved adhesion to metal substrates and/or fiber reinforcement and in the preparation of copolymers for use as blend compatabilizers.
  • arylene sulfide polymer is defined by the formula wherein -Ar-S- is the repeating unit, i is the number of repeating units in the polymer molecule, and Ar is selected from the group consisting of wherein each R is selected from the group consisting of hydrogen and alkyl radicals having 1 to about 4 carbon atoms, the total number of carbon atoms in all of the R groups in the repeat unit being 0 to about 12.
  • extrusion rate refers to a flow rate measurement on molten polymer based on ASTM D 1238-86, Condition 315/0.345, modified to use an orifice having a length of 31.8 mm and a 5 minute preheat time.
  • extrusion rate is a specific type of melt flow measurement which is particularly useful in characterizing arylene sulfide polymers in the lower molecular weight range.
  • inherent viscosity refers to dilute solution viscosity which is the ratio of the natural logarithm of the relative viscosity to the polymer solution concentration in grams per deciliter.
  • the relative viscosity is the ratio of the flow time of a specific solution of the polymer to the flow time of the pure solvent.
  • inherent viscosities for arylene sulfide polymers are measured generally according to the method described in ASTM D 1243-79 wherein samples of dried polymer are dissolved in 1-chloronaphthalene at 210°C at a polymer concentration of 0.4 grams per deciliter (g/dL) utilizing a No. 50 Cannon-Fenske viscometer.
  • inherent viscosity is a measurement which is a function of molecular weight and which is particularly useful in characterizing arylene sulfide polymers in the lower molecular weight range.
  • Suitable olefins which are utilized according to the invention are selected from the group consisting of alkenes having 2 to about 20 carbon atoms, dienes having 2 to about 20 carbon atoms, functionalized alkenes represented by the formulas and and functionalized dienes represented by the formula wherein R' is selected from the group consisting of hydrogen and alkyl groups having 1 to about 10 carbon atoms, R" is selected from the group consisting of
  • R"' is selected from the group consisting of -H and -CH3
  • Y is selected from the group consisting of -H and -COO ⁇
  • m is 0 or 1
  • n is 0 to 10
  • p is 0 or 1
  • Y, n and R" in any of the above formulas may be the same or different and wherein the total number of carbon atoms in the functionalized alkene of formula (II) and the functionalized diene is from 2 to about 20 and the total number of carbon atoms in the functionalized alkene of formula (I) is 3 or 4.
  • a Y group of COO ⁇ can be obtained by addition of the corresponding carboxylate salt or it can be prepared in-situ by reaction of the free carboxylic acid with a stoichiometric amount of a base, e.g. an alkali metal hydroxide.
  • a base e.g. an alkali metal hydroxide.
  • the alkenes, dienes, functionalized alkenes of formula (II) and functionalized dienes which are employed according to the invention are compounds having 2 to about 20 carbon atoms per molecule, preferably about 4 to about 9 carbon atoms per molecule, and most preferably about 5 to about 7 carbon atoms per molecule.
  • Suitable olefins which can be employed in the process of the invention include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-nonene, 2-butene, 3-methyl-1-butene, 1,3-butadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 2-methyl-1,3-butadiene, 3-butenoic acid, 4-pentenenitrile, 4-penten-1-ol, 4-methyl-3-penten-2-one, 5-amino-4-methyl-1-hexene, 2-methyl-6-methylamino-2-heptene and 6-methyl-5-hepten-2-one, and the like, and mixtures of any two or more thereof.
  • the presently preferred compounds are 1-heptene, 1,5-hexadiene, 1-nonene, and 3-butenoic acid because of their effectiveness.
  • the amount of olefin employed according to the process of the invention can be conveniently expressed in terms of a molar ratio based on the sulfur source.
  • the molar ratio of olefin to sulfur source will be about 0.02:1 to about 0.3:1, preferably about 0.05:1 to about 0.25:1, and most preferably about 0.1:1 to about 0.2:1.
  • the olefin will be effective in the process of the invention when added to the polymerization mixture prior to subjecting the polymerization mixture to polymerization conditions, or during the time the polymerization mixture is being subjected to polymerization conditions. If an aqueous sulfur-containing compound is used and a dehydration step is required, the olefin may only be added prior to dehydration if the olefin is not volatile under dehydration conditions.
  • the dihaloaromatic compounds which are employed according to the invention are compounds having 6 to about 22 carbon atoms per molecule.
  • the halogen substituent on the dihaloaromatic compound can be selected from the group consisting of chlorine, bromine and iodine.
  • the dihaloaromatic compound will be dihalo-substituted benzene and more preferably dichloro-substituted benzene.
  • the dihaloaromatic compound is selected from the group consisting of p-dichlorobenzene and mixtures of p-dichlorobenzene with a total of about 0 to about 10 mole percent of at least one of m-dichlorobenzene, o-dichlorobenzene and alkyl-substituted dichlorobenzene having the formula wherein R is as defined herein and at least one R is not hydrogen.
  • dihaloaromatic compounds examples include p-dichlorobenzene, p-dibromobenzene, p-diiodobenzene, 1-chloro-4-bromobenzene, 1-chloro-4-iodobenzene, 1-bromo-4-iodobenzene, 2,5-dichlorotoluene, 2,5-dichloro-p-xylene, 1-ethyl-4-isopropyl-2,5-dibromobenzene, 1,2,4,5-tetramethyl-3,6-dichlorobenzene, 1,2,4,5-tetrabutyl-3,6-dichlorobenzene, 1-ethyl-3-butyl-2,5-dichlorobenzene, 1-ethyl-2,5-diiodobenzene, 1-butyl-2,5-dichlorobenzene, 1-butyl-4-ethyl-2,5-ddi
  • the cyclic organic amide used in the process of the invention should be substantially liquid at the reaction temperatures and pressures employed.
  • the cyclic organic amides can have 5 to about 12 carbon atoms per molecule.
  • suitable cyclic organic amides include N,N'-ethylenedipyrrolidone, N-methyl-2-pyrrolidone, pyrrolidone, caprolactam, N-ethyl caprolactam, N-methyl caprolactam and mixtures thereof.
  • the presently preferred cyclic organic amide is N-methyl-2-pyrrolidone because of its effectiveness and commercial availability.
  • the amount of cyclic organic amide employed according to the process of the invention can be expressed in terms of a molar ratio of cyclic organic amide to sulfur source compounds. Broadly, the molar ratio of cyclic organic amide to sulfur source compound will be about 1.5:1 to about 25:1, preferably about 2:1 to about 8:1.
  • suitable sulfur sources which can be employed in the production of the arylene sulfide polymers include alkali metal sulfides, alkali metal bisulfides, N-methyl-2-pyrrolidinethione, and hydrogen sulfide.
  • the alkali metal sulfides can be employed with good results in the absence of any added alkali metal hydroxide whereas the other suitable sulfur sources are preferably employed in the process of the invention in the presence of an added alkali metal hydroxide.
  • the amount of added alkali metal hydroxide will generally be in the range of from about 0.3:1 to about 4:1, preferably about 0.4:1 to about 2:1 moles per mole of alkali metal bisulfides or N-methyl-2-pyrrolidinethione.
  • the amount of added alkali metal hydroxide is generally within the range of about 1.3:1 to about 5:1 preferably about 1.4:1 to about 3:1 moles per mole of hydrogen sulfide employed.
  • Alkali metal bisulfides that can be employed according to the invention include sodium bisulfide, lithium bisulfide, potassium bisulfide, rubidium bisulfide, cesium bisulfide, and mixtures thereof.
  • Sodium bisulfide is preferred because of ready availability and good results obtained therewith.
  • the alkali metal bisulfide can conveniently be utilized in the process of the invention as an aqueous solution. For example, an aqueous solution of sodium bisulfide having about 60 weight percent sodium bisulfide is convenient to use.
  • Alkali metal sulfides which can be employed in the process of the invention include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide, and mixtures thereof.
  • the alkali metal sulfide can be used in anhydrous form, as a hydrate, or as an aqueous mixture.
  • Sodium sulfide is preferred because of ready availability and good results obtained therewith.
  • the ratio of reactants for the preparation of arylene sulfide polymers according to the invention can vary considerably, the ratio of moles of dihaloaromatic compound to atoms of divalent sulfur in the sulfur source should be within the range of about 0.8:1 to about 2:1, preferably about 0.95:1 to about 1.3:1.
  • a polymerization modifier such as an alkali metal carboxylate can be employed in the process of the invention particularly when the olefin utilized is a functionalized alkene or a functionalized diene.
  • the alkali metal carboxylates that can be employed in the process of the invention can be represented by the formula R''''CO2M where R'''' is a hydrocarbyl radical selected from alkyl, cycloalkyl, and aryl and combinations thereof such as alkaryl, aralkyl, and the like, the number of carbon atoms in said R'''' being within the range of 1 to about 20, and M is an alkali metal selected from lithium, sodium, potassium, rubidium, and cesium.
  • alkali metal carboxylates examples include lithium acetate, sodium acetate, potassium acetate, lithium propionate, sodium propionate, lithium 2-methylpropionate, rubidium butyrate, lithium valerate, sodium valerate, cesium hexanoate, lithium heptanoate, lithium 2-methyl octanoate, potassium dodecanoate, rubidium 4-ethyltetradecanoate, sodium octadecanoate, sodium heneicosanoate, lithium cyclohexane carboxylate, cesium cyclododecane carboxylate, sodium 3-methylcyclopentane carboxylate, potassium cyclohexylacetate, potassium benzoate, lithium benzoate, sodium benzoate, potassium m-toluate, lithium phenylacetate, sodium 4-phenylcyclohexane carboxylate, potassium p-tolylacetate, lithium 4-ethylcyclohexyla
  • the amount of alkali metal carboxylate employed according to the invention can be expressed in terms of molar ratio based on the sulfur source compound employed. Broadly, the molar ratio of alkali metal carboxylate to sulfur source compound will be from about 0.002:1 to about 4:1, preferably about 0.1:1 to about 2:1.
  • the alkali metal carboxylate can be used in anhydrous form, as a hydrate, or as an aqueous mixture.
  • Suitable polymerization conditions include a reaction temperature which can vary over a wide range but will generally be within the range of about 200°C to about 450°C, preferably from about 210°C to about 350°C.
  • the reaction time will be within the range of about 10 minutes to about 72 hours and preferably about 1 hour to about 8 hours.
  • the pressure need only be sufficient to maintain the dihaloaromatic compound and the cyclic organic amide substantially in the liquid phase, and to substantially retain the sulfur source therein.
  • the flashed reaction mixture residue can be slurried with a liquid diluent such as water in which the alkali metal halides and other impurities are soluble.
  • a liquid diluent such as water in which the alkali metal halides and other impurities are soluble.
  • the liquid diluent is removed with dissolved impurities such as by filtration leaving a particular arylene sulfide polymer. This washing process can be repeated until the desired level of arylene sulfide polymer purity is attained.
  • Another known method that can be employed is the "water quench" process described in US-A-4,415,729, wherein the polymerization mixture is contacted at a temperature above that at which the arylene sulfide polymer is soluble in the polymerization mixture with a sufficient amount of a separation agent that is soluble in the cyclic organic amide and is a non-solvent for the arylene sulfide polymer, e.g. water, to cause or enhance a phase separation.
  • a separation agent that is soluble in the cyclic organic amide and is a non-solvent for the arylene sulfide polymer, e.g. water
  • phase-separated mixture produces a slurry of particulate arylene sulfide polymer in the cyclic organic amide which can be filtered to recover the particulate arylene sulfide polymer.
  • the separated polymer can be washed as described above.
  • the arylene sulfide polymer will comprise end groups selected from the group consisting of alkyl radicals having 2 to about 20 carbon atoms, alkenyl radicals having 2 to about 20 carbon atoms, functionalized alkyl radicals derived from the formula (I) having 3 or 4 carbon atoms, functionalized alkyl radicals derived from the formula (II) having 2 to about 20 carbon atoms, functionalized alkenyl radicals having 2 to about 20 carbon atoms and combinations thereof wherein the end groups are a result of the use of olefins as defined herein according to the process of the invention.
  • arylene sulfide polymer composition end groups will comprise structures selected from the group consisting of and combinations thereof wherein m, n, p, R', R", R"' and Y are as defined herein and Y, n and R" in any of end groups (III) - (X) may be the same or different, and wherein the total number of carbon atoms in the end groups of formulas (III) and (IV) is 3 or 4, and the total number of carbon atoms in the end groups of formulas (V), (VI), (VII), (VIII), (IX) and (X) is 2 to about 20.
  • Polymer thermal transitions were determined by differential scanning calorimetry (DSC) on a Perkin-Elmer DSC, Model DSC-2, with a nitrogen atmosphere at a sample heating rate of 20°C/min.
  • the polymer glass transition (Tg) and melting point (Tm) are reported as °C.
  • Polymer ash levels were determined by burning a weighed sample of the polymer in a platimum dish. Residual carbonaceous material was removed by heating the residue at 540°C in a muffle furnace. The weight of the residue (ash) is expressed as a percentage of the original weight of the polymer.
  • the polymer chlorine content was determined by neutron activation, with the results reported as weight percent chlorine based on the original sample weight.
  • Fourier transform infrared (FTIR) spectra were determined using film pressed from the polymer without heat. The presence of alkyl groups was indicated by a peak at approximately 2925 cm-1.
  • This example is a control run in which PPS is made without the addition of an olefin.
  • a one-liter, stainless steel reactor was charged with 1.00 g-mol of sodium hydrosulfide (NaSH) as an aqueous mixture containing about 60 weight percent NaSH, 1.03 g-mol sodium hydroxide (NaOH) as a solid, and 2.5 g-mol N-methyl-2-pyrrolidone (NMP).
  • NaSH sodium hydrosulfide
  • NaOH sodium hydroxide
  • NMP N-methyl-2-pyrrolidone
  • PPS polymerization run 3 was carried out in a manner similar to that described in Example 2 except that the dehydrated mixture was charged with 0.515 g-mol meta-DCB and 0.515 g-mol para-DCB with the 0.25 g-mol 1-nonene and NMP. In this polymerization, the polymerization mixture was held at 235°C for one hour and at 265°C for two hours.
  • the product of this polymerization was a copolymer recovered in a yield of 56 mole percent with an IV of 0.06 dL/g.
  • the polymer Tg was about 25° C.
  • Carbon-13 NMR spectra of the copolymer in benzene and tetrahydrofuran (THF) showed that the polymer contained alkyl groups.
  • Example 2 After the reaction had been exposed to conditions noted in Example 1, the addition of a large quantity of water to the mixture revealed that no polyolefin was formed as evidenced by the lack of a precipitate forming upon addition of the water. The conditions used for the PPS polymerization do not produce any significant amounts of polyolefins from the added olefins.
  • the extrusion rates of polymers 6 and 7 are higher than for control run 5. IR spectra of polymers 6 and 7 show that alkyl groups are present in the polymer. The presence of sodium acetate in run 7 does not significantly effect the polymer molecular weight. 1-Heptene added to a PPS polymerization is incorporated into the polymer and reduces the PPS melt viscosity.
  • An invention run was carried out with an unsaturated carboxylic acid added to the polymerization to determine the effect of unsaturated carboxylic acid salts on PPS polymerizations.
  • control run 8 0.25 g-mol of 4-pentenoic acid was charged with the NaSH. NaOH and NMP before dehydration in a polymerization procedure similar to that described for run 5 in Example 5.
  • invention run 9 0.29 g-mol 3-butenoic acid was charged with the NaSH, NaOH and NMP before dehydration. Both polymerizations were carried out for one hour at 235°C and three hours at 265°C. Additional NaOH was used in these polymerization runs for neutralization of the acid groups. The chemicals used and the results of these two runs are summarized in Table II. Run 5 from Example 5 is included in the table for comparison.
  • Control run 8 with 4-pentenoic acid did not produce a decrease in the polymer melt viscosity.
  • An FTIR spectrum of the polymer from run 8 showed no alkyl groups to be present while an FTIR spectrum of the polymer from run 9 did show the presence of alkyl groups.
  • Run 10 is a control run made in a titanium reactor without any added 1-heptene and with polymerization conditions of one hour at 235°C and two hours at 265°C.
  • Run 11 is an invention run made in a 316 stainless steel reactor with 0.25 g-mol 1-heptene and polymerization conditions of three hours at 245°C.
  • Runs 12 through 16 all used a titanium reactor and 0.25 g-mol 1-heptene. 0.30 g-mol of NaOAc was also present in run 16.
  • the polymerization conditions for run 12 were three hours at 245°C; run 13, 2.5 hours at 255°C; run 14, 4 hours at 235°C; run 15, two hours at 265°C; and run 16, three hours at 265°C.
  • Table III The chemicals used and the results of these runs are summarized in Table III.
  • PPS polymerization run 17 was carried out in a manner similar to that described in run 11 of Example 7 except that 0.10 g-mol of 1,5-hexadiene was added to the dehydrated mixture instead of 1-heptene.
  • a control PPS polymerization was carried out to produce a truly low molecular weight PPS for comparison with the products of the invention runs above.
  • Run 18 was carried out in a procedure similar to that described in Example 1 except that the reactor was charged with 0.5 g-mol NaSH, 0.5 g-mol NaOH, and 1.25 g-mol NMP. The dehydrated mixture was charged with 1.03 g-mol DCB and 1.0 g-mol NMP. Due to the large excess of DCB over the sulfur source, a very low molecular weight PPS was produced. Polymer 18 was recovered in 94 mole percent yield and had a degree of polymerization of about 13 as determined by 13C NMR.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Claims (12)

  1. Verfahren zur Herstellung von Arylensulfidpolymeren, das folgende Stufen umfaßt:
    (a) Kontaktieren mindestens einer Schwefelquelle, mindestens eines cyclischen organischen Amids und mindestens einer aromatischen Dihalogenverbindung unter Bildung eines Polymerisationsgemisches;
    (b) Unterwerfen des Polymerisationsgemisches unter eine Polymerisation; und
    (c) Gewinnung des Arylensulfidpolymeren;
    wobei das Verfahren in Gegenwart eines Olefins durchgeführt wird, das unter Alkenen mit 2 bis 20 Kohlenstoffatomen, Dienen mit 2 bis 20 Kohlenstoffatomen, funktionalisierten Alkenen mit der Formel:
    Figure imgb0043
     funktionalisierten Alkenen mit der Formel:
    Figure imgb0044
     und funktionalisierten Dienen mit der Formel:
    Figure imgb0045
     ausgewählt ist, wobei R' unter Wasserstoff und Alkylgruppen mit 1 bis 10 Kohlenstoffatomen ausgewählt ist, R" unter
       -H, -CN, -NR'₂, -NO₂, -Aryl,
    Figure imgb0046
        -OR',
    Figure imgb0047
        -PO₃H, -SO₃H, -SO₂R',
    Figure imgb0048
        -PR'₂,
    Figure imgb0049
        und -SiR'₃
    ausgewählt ist, R"' unter -H und -CH₃ ausgewählt ist, Y unter -H und -COO⁻ ausgewählt ist, m den Wert 0 oder 1 hat, n einen Wert von 0 bis 10 hat, p den Wert 0 oder 1 hat und Y, n und R" in jeder der vorstehenden Formeln gleich oder verschieden sein können und wobei die Gesamtzahl der Kohlenstoffatome in dem funktionalisierten Alken der Formel (II) und dem funktionalisierten Dien 2 bis 20 beträgt und die Gesamtzahl der Kohlenstoffatome in dem funktionalisierten Alken der Formel (I) 3 oder 4 beträgt.
  2. Verfahren nach Anspruch 1, wobei das molare Verhältnis des Olefins zur Schwefelquelle 0,02:1 bis 0,3:1 beträgt.
  3. Verfahren nach Anspruch 1 oder 2, wobei das Olefin zu dem Polymerisationsgemisch gegeben wird, bevor das Polymerisationsgemisch der Polymerisation unterworfen wird.
  4. Verfahren nach Anspruch 1 oder 2, wobei das Olefin während der Zeit, in der das Polymerisationsgemisch der Polymerisation unterworfen wird, zugegeben wird.
  5. Verfahren nach Anspruch 3 oder 4, wobei die Schwefelquelle unter Alkalimetallsulfiden, Alkalimetallbisulfiden, N-Methyl-2-pyrrolidinthion und Schwefelwasserstoff ausgewählt ist.
  6. Verfahren nach Anspruch 5, wobei das Polymerisationsgemisch ferner ein Alkalimetallhydroxid umfaßt.
  7. Verfahren nach Anspruch 6, wobei das cyclische organische Amid N-Methyl-2-pyrrolidon umfaßt und die aromatische Dihalogenverbindung unter p-Dichlorbenzol und Gemischen von p-Dichlorbenzol mit insgesamt bis zu etwa 10 Mol-% mindestens eines der Bestandteile m-Dichlorbenzol, o-Dichlorbenzol und alkylsubstituierten Dichlorbenzolen mit der Formel
    Figure imgb0050
     worin R Wasserstoff oder eine Alkylgruppe mit 1 bis 4 Kohlenstoffatomen darstellt und mindestens einer der Reste R nicht Wasserstoff ist, ausgewählt ist.
  8. Verfahren nach Anspruch 7, wobei das Alkalimetallbisulfid Natriumbisulfid umfaßt, das Alkalimetallhydroxid Natriumhydroxid umfaßt und die aromatische Dihalogenverbindung p-Dichlorbenzol umfaßt.
  9. Verfahren nach einem der vorstehenden Ansprüche, wobei das Polymerisationsgemisch ferner ein Alkalimetallcarboxylat umfaßt.
  10. Verfahren zur Herstellung von Poly-(phenylensulfid), das folgende Stufen umfaßt:
    (a) Dehydratisieren eines wäßrigen Gemisches, das Natriumbisulfid, Natriumhydroxid und N-Methyl-2-pyrrolidon umfaßt, unter Bildung eines dehydratisierten Gemisches;
    (b) Kontaktieren von p-Dichlorbenzol mit dem dehydratisierten Gemisch unter Bildung eines Polymerisationsgemisches;
    (c) Unterwerfen des Polymerisationsgemisches einer Polymerisation; und
    (d) Gewinnung des Poly-(phenylensulfids);

       wobei das Verfahren in Gegenwart eines Olefins durchgeführt wird, das unter 1-Hepten, 1-Nonen, 1,5-Hexadien und 3-Butensäure ausgewählt ist.
  11. Arylensulfidpolymer, umfassend Endgruppen, die unter
    Figure imgb0051
    Figure imgb0052
    Figure imgb0053
    Figure imgb0054
    Figure imgb0055
    Figure imgb0056
    Figure imgb0057
    Figure imgb0058
     und Kombinationen davon ausgewählt sind, wobei R' unter Wasserstoff und Alkylgruppen mit 1 bis 10 Kohlenstoffatomen ausgewählt ist, R" unter
       -H, -CN, -NR'₂, -NO₂, -Aryl,
    Figure imgb0059
        -OR',
    Figure imgb0060
        -PO₃H, -SO₃H, -SO₂R',
    Figure imgb0061
        -PR'₂,
    Figure imgb0062
        und -SiR'₃
    ausgewählt ist, R"' unter -H und -CH₃ ausgewählt ist, Y unter -H und -COO⁻ ausgewählt ist, m den Wert 0 oder 1 hat, n einen Wert von 0 bis 10 hat, p den Wert 0 oder 1 hat und Y, n und R" in jeder der vorstehenden Endgruppen gleich oder verschieden sein können und wobei die Gesamtzahl der Kohlenstoffatome in den Endgruppen der Formeln (III) und (IV) 3 oder 4 beträgt und die Gesamtzahl der Kohlenstoffatome in den Endgruppen der Formeln (V), (VI), (VII), (VIII), (IX) und (X) 2 bis 20 beträgt.
  12. Polymer nach Anspruch 11, wobei es sich bei dem Arylensulfidpolymeren um Poly-(phenylensulfid) handelt.
EP91119960A 1990-11-23 1991-11-22 Verfahren zur Herstellung von Arylensulfidpolymer Expired - Lifetime EP0487103B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US617228 1990-11-23
US07/617,228 US5115093A (en) 1990-11-23 1990-11-23 Process for preparing arylene sulfide polymers in the presence of functionalized olefin

Publications (2)

Publication Number Publication Date
EP0487103A1 EP0487103A1 (de) 1992-05-27
EP0487103B1 true EP0487103B1 (de) 1996-01-10

Family

ID=24472788

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91119960A Expired - Lifetime EP0487103B1 (de) 1990-11-23 1991-11-22 Verfahren zur Herstellung von Arylensulfidpolymer

Country Status (11)

Country Link
US (1) US5115093A (de)
EP (1) EP0487103B1 (de)
JP (1) JP2690228B2 (de)
KR (1) KR920009876A (de)
AT (1) ATE132880T1 (de)
CA (1) CA2052015A1 (de)
DE (1) DE69116320T2 (de)
DK (1) DK0487103T3 (de)
ES (1) ES2082102T3 (de)
GR (1) GR3018917T3 (de)
TW (1) TW215096B (de)

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3354129A (en) * 1963-11-27 1967-11-21 Phillips Petroleum Co Production of polymers from aromatic compounds
US3800845A (en) * 1971-12-14 1974-04-02 Phillips Petroleum Co Solvent removal from poly(arylene sulfide) reaction slurry
US4337182A (en) * 1981-03-26 1982-06-29 Phillips Petroleum Company Poly (arylene sulfide) composition suitable for use in semi-conductor encapsulation
US4415729A (en) * 1982-06-04 1983-11-15 Phillips Petroleum Company Recovering granular poly(arylene sulfide) particles from a poly(arylene sulfide) reaction mixture
US4482665A (en) * 1982-09-14 1984-11-13 Phillips Petroleum Company Encapsulation of electronic components with calcium silicate-containing poly(arylene sulfide) compositions
DE3421608A1 (de) * 1984-06-09 1985-12-12 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung von polyarylensulfiden mit funktionellen endgruppen
EP0228268B1 (de) * 1985-12-27 1990-05-23 Toray Industries, Inc. Polyphenylensulfidharzzusammensetzung und Verfahren zu ihrer Herstellung
US4786711A (en) * 1987-01-23 1988-11-22 Phillips Petroleum Company P-phenylene sulfide polymer preparation with dehydrated mixture of alkali metal hydroxide and excess alkali metal bisulfide
US4767841A (en) * 1987-02-24 1988-08-30 Phillips Petroleum Company Arylene sulfide polymer preparation from dehydrated admixture comprising sulfur source, cyclic amide solvent and water
US4820800A (en) * 1988-02-25 1989-04-11 Phillips Petroleum Company Arylene sulfide polymers
EP0384191A3 (de) * 1989-02-07 1991-09-18 Mitsubishi Rayon Company, Ltd. Poly(arylensulfid)-Harzzusammensetzung

Also Published As

Publication number Publication date
ATE132880T1 (de) 1996-01-15
GR3018917T3 (en) 1996-05-31
TW215096B (de) 1993-10-21
JP2690228B2 (ja) 1997-12-10
CA2052015A1 (en) 1992-05-24
KR920009876A (ko) 1992-06-25
DE69116320D1 (de) 1996-02-22
DE69116320T2 (de) 1996-05-23
JPH04292626A (ja) 1992-10-16
ES2082102T3 (es) 1996-03-16
US5115093A (en) 1992-05-19
DK0487103T3 (da) 1996-02-19
EP0487103A1 (de) 1992-05-27

Similar Documents

Publication Publication Date Title
US4038259A (en) Production of p-phenylene sulfide polymers
EP0280274B1 (de) Polyarylensulfide
US4096132A (en) Production of p-phenylene sulfide polymers
US4748231A (en) Reprecipitation of poly(arylene sulfide) to increase molecular weight thereof
US4089847A (en) Temperature programming in the production of arylene sulfide polymers
EP0513730B1 (de) Verfahren zur Herstellung von Arylensulfidpolymeren
CA2096652C (en) Process for the preparation of poly(arylene sulfide) with low metal contamination and polymer produced
US5175243A (en) Process for preparing arylene sulfide polymers with halo benzene containing deactivating group
EP0086487B1 (de) Verfahren zur Herstellung von Arylensulfidpolymeren
US5235032A (en) Process for the preparation of poly(arylene sulfide) with low metal contamination
US5328980A (en) Method of preparing poly(arylene sulfide) polymers, polymers and polymer blends
US5053486A (en) Process for preparing poly(arylene sulfide sulfone) with controlled ratio of alkali metal carboxylate to sulfur source
JPS63243133A (ja) 硫化アリーレン重合体の製法
EP0487103B1 (de) Verfahren zur Herstellung von Arylensulfidpolymer
US4988796A (en) Process for preparing poly(arylene sulfide sulfone)
US5144004A (en) Process for preparing arylene sulfide sulfone/sulfoxide polymers
KR0182327B1 (ko) 폴리(페닐렌설파이드) 중합체의 제조 방법
US5003033A (en) Process for preparing branched poly(arylene sulfide ketone)
JPH04275334A (ja) フェニレンスルフィドポリマーの製造法
US5064936A (en) Process for preparing high extrusion rate arylene sulfide polymers
US5331069A (en) Method of treating poly(arylene sulfide sulfone) polymers and polymers
US4882416A (en) Preparation of poly arylene sulfide with specified ratio of sulfur source to cyclic organic amide
EP0534359A1 (de) Herstellungsverfahren für Polyarylensulfide
US5177174A (en) Branched aromatic sulfide/sulfone polymer production
EP0431613A2 (de) Verfahren zur Herstellung von Polyarylensulfidsulfonen

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LI LU NL SE

17P Request for examination filed

Effective date: 19920929

17Q First examination report despatched

Effective date: 19950216

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LI LU NL SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19960110

REF Corresponds to:

Ref document number: 132880

Country of ref document: AT

Date of ref document: 19960115

Kind code of ref document: T

ITF It: translation for a ep patent filed
REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

REF Corresponds to:

Ref document number: 69116320

Country of ref document: DE

Date of ref document: 19960222

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: KIRKER & CIE SA

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2082102

Country of ref document: ES

Kind code of ref document: T3

ET Fr: translation filed
REG Reference to a national code

Ref country code: GR

Ref legal event code: FG4A

Free format text: 3018917

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19961122

Ref country code: DK

Effective date: 19961122

Ref country code: AT

Effective date: 19961122

REG Reference to a national code

Ref country code: DK

Ref legal event code: EBP

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19961123

Ref country code: ES

Free format text: LAPSE BECAUSE OF THE APPLICANT RENOUNCES

Effective date: 19961123

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19961130

Ref country code: LI

Effective date: 19961130

Ref country code: CH

Effective date: 19961130

Ref country code: BE

Effective date: 19961130

26N No opposition filed
BERE Be: lapsed

Owner name: PHILLIPS PETROLEUM CY

Effective date: 19961130

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19970601

REG Reference to a national code

Ref country code: GR

Ref legal event code: MM2A

Free format text: 3018917

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19961122

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19970731

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 19970601

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19970801

EUG Se: european patent has lapsed

Ref document number: 91119960.2

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20010402

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20051122